Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/84—Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
  • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general

Definitions

• the present invention relates to a dental curable composition and a method for producing a dental curable composition.
• a flowable composite resin generally contains a polymerizable monomer and an inorganic filler, and is frequently used as a material for filling and repairing tooth defects and caries.
• Patent Document 1 discloses an amorphous form having an average particle diameter of 0.1 to 0.3 ⁇ m, which is surface-treated with a polymerizable monomer (A) and a specific silane coupling agent (a) as a dental curable composition.
• a dental curable composition containing inorganic particles (B) and inorganic ultrafine particles (C) having an average particle diameter of 5 to 50 nm and surface-treated with a specific silane coupling agent (b) is disclosed.
• the dental curable composition contains 92.5 to 98% by weight and 2 to 7.5% by weight of the amorphous inorganic particles (B) and the inorganic ultrafine particles (C), respectively, in the total amount of the inorganic particles.
• the consistency of the dental curable composition is 25 to 55.
• One aspect of the present invention is to provide a flowable composite resin capable of simultaneously satisfying polishing properties, wear resistance, shapeability / operability, and bending strength in view of the problems of the above-described conventional technology.
• One embodiment of the present invention is a dental curable composition
• a dental curable composition comprising a polymerizable monomer, inorganic particles (A) and inorganic particles (B), wherein the inorganic particles (A) are represented by the general formula:
• R 1 is a hydrogen atom or a methyl group
• R 2 is a group capable of hydrolysis
• R 3 is a hydrocarbon group having 1 to 6 carbon atoms
• p Is 2 or 3 is an integer of 8 to 13.
• the volume-median particle size is 0.1 ⁇ m or more and 0.9 ⁇ m or less
• the inorganic particles (B) are represented by the general formula:
• R 4 and R 5 are each independently a methyl group or an ethyl group.
• R 6 , R 7 and R 5 are each independently a methyl group or an ethyl group.
• the average primary particle size is 5 nm or more and 50 nm or less
• One aspect of the present invention includes a step of mixing a polymerizable monomer, inorganic particles (A) and inorganic particles (B) in the method for producing a dental curable composition, wherein the inorganic particles (A) General formula
• R 1 is a hydrogen atom or a methyl group
• R 2 is a group capable of hydrolysis
• R 3 is a hydrocarbon group having 1 to 6 carbon atoms
• p Is 2 or 3 is an integer of 8 to 13.
• the volume-median particle size is 0.1 ⁇ m or more and 0.9 ⁇ m or less
• the inorganic particles (B) are represented by the general formula:
• R 4 and R 5 are each independently a methyl group or an ethyl group.
• R 6 , R 7 and R 5 are each independently a methyl group or an ethyl group.
• the average primary particle size is 5 nm or more and 50 nm or less
• the dental curable composition contains a polymerizable monomer, inorganic particles (A), and inorganic particles (B).
• the inorganic particles (A) are surface-treated with a compound represented by the general formula (1). For this reason, it is possible to achieve both the bending strength, the formability and the operability of the flowable composite resin.
• the volume median particle size of the inorganic particles (A) is 0.1 to 0.9 ⁇ m, preferably 0.15 to 0.70 ⁇ m.
• the volume-median particle size of the inorganic particles (A) is less than 0.1 ⁇ m, the consistency of the flowable composite resin is lowered, and when it exceeds 0.9 ⁇ m, the wear resistance, abrasiveness and shapeability of the flowable composite resin are reduced. ⁇ Operability is reduced.
• the volume median particle size of the inorganic particles (A) can be measured by a laser diffraction scattering method.
• the average primary particle size of the inorganic particles (B) is 5 to 50 nm, preferably 5 to 20 nm. If the average primary particle size of the inorganic particles (B) is less than 5 nm, the production becomes difficult, and if it exceeds 50 nm, the formability and operability of the flowable composite resin are lowered.
• the average primary particle size of the inorganic particles (B) is an average value of the primary particle sizes of 100 inorganic particles (B) randomly selected by taking an electron micrograph.
• the ratio of the mass of the inorganic particles (B) to the total mass of the inorganic particles (A) and the inorganic particles (B) is 0.02 to 0.05.
• the ratio of the mass of the inorganic particles (B) to the total mass of the inorganic particles (A) and the inorganic particles (B) is less than 0.02 or more than 0.05, the formability / operation of the flowable composite resin Sex is reduced.
• the refractive index after polymerization of the polymerizable monomer is usually 1.52 to 1.58, preferably 1.53 to 1.58.
• a refractive index means the refractive index measured using an Abbe refractometer at 25 degreeC.
• the polymerizable monomer is preferably a radical polymerizable monomer.
• the polymerizable monomer is not particularly limited, but esters such as ⁇ -cyanoacrylic acid, (meth) acrylic acid, ⁇ -haloacrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, itaconic acid, (Meth) acrylamide, (meth) acrylamide derivatives, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, styrene derivatives and the like may be mentioned, and two or more may be used in combination. Among these, (meth) acrylic acid esters and (meth) acrylamide derivatives are preferable, and (meth) acrylic acid esters are more preferable.
• Monofunctional (meth) acrylic acid esters and (meth) acrylamide derivatives include methyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2,3-dibromopropyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, erythritol mono (meta) ) Acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- (dihydroxyethyl) (meth) acrylamide, (meth) acryloyl oxide decylpi Pyridinium bromide, (meth) acryloy
• Bifunctional (meth) acrylic acid esters include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2,2-bis [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] propane, 2,2 -Bis [4- (2- (meth) acryloyloxyethoxy) phenyl] propane, 2,2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, 1,2-bis [3- (meth) acryloyl Oxy-2-hydroxypropoxy] ethane, pentaeryth Ritoruji (meth) acrylate, [2,2,4-trimethylhe
• Trifunctional or higher (meth) acrylic acid esters include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, N, N ′-(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, 1,7-diacryloyloxy -2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane and the like.
• the mass ratio of the polymerizable monomer to the total mass of the inorganic particles (A) and the inorganic particles (B) is usually 0.25 to 0.5, and preferably 0.3 to 0.45.
• the inorganic particles (A) may be spherical, but are preferably indefinite. Thereby, since the specific surface area of an inorganic particle (A) increases, bondability with a polymerizable monomer becomes strong and bending strength can be improved.
• R 2 in the general formula (1) is not particularly limited, a methoxy group, an ethoxy group, an alkoxy group or a butoxy group, a chlorine atom, a isocyanate group.
• R 3 in the general formula (1) is not particularly limited, and examples thereof include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an alkynyl group having 2 to 6 carbon atoms.
• the alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic, and is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. , Sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
• the alkenyl group having 2 to 6 carbon atoms may be linear, branched or cyclic, and is vinyl, allyl, methylvinyl, butenyl, pentenyl, hexenyl, cyclopropenyl. Group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group and the like.
• the alkynyl group having 2 to 6 carbon atoms may be linear, branched or cyclic, and is an ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 1-methyl- 2-propynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 1-ethyl-2-propynyl group, 2-pentynyl group, 3-pentynyl group, 1-methyl-2-butynyl group, 4- Pentynyl group, 1-methyl-3-butynyl group, 2-methyl-3-butynyl group, 1-hexynyl group, 2-hexynyl group, 1-ethyl-2-butynyl group, 3-hexynyl group, 1-methyl-2 -Pentynyl group, 1-methyl-3-pentynyl group, 4-methyl-1-pentynyl group, 3-methyl-1
• the compound represented by the general formula (1) is not particularly limited, but 8-methacryloyloxyoctyltrimethoxysilane, 9-methacryloyloxynonyltrimethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 11-methacryloyloxyun.
• Decyltrimethoxysilane 11-methacryloyloxyundecyldichloromethylsilane, 11-methacryloyloxyundecyltrichlorosilane, 11-methacryloyloxyundecyldimethoxymethylsilane, 12-methacryloyloxidedecyltrimethoxysilane, 13-methacryloyloxytridecyltri A methoxysilane etc. are mentioned, You may use 2 or more types together.
• 8-methacryloyloxyoctyltrimethoxysilane 9-methacryloyloxynonyltrimethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, and 11-methacryloyloxyundecyltrimethoxysilane are preferable.
• the compound represented by General formula (1) is diluted with a solvent, stirring the inorganic particle (A) before surface treatment with a mixing tank. The solution obtained was sprayed and heated and dried in a bath for a certain period of time while continuing stirring. The inorganic particles (A) before surface treatment and the compound represented by the general formula (1) were stirred and mixed in a solvent. Then, the method of heat-drying etc. are mentioned.
• the mass ratio of the compound represented by the general formula (1) to the inorganic particles (A) before the surface treatment is usually 0.005 to 0.15, and 0.01 to 0.13. preferable.
• the refractive index of the inorganic particles (A) is usually 1.52 to 1.58, preferably 1.53 to 1.58.
• the difference between the refractive index after polymerization of the polymerizable monomer and the refractive index of the inorganic particles (A) is usually 0.03 or less.
• the material constituting the inorganic particles (A) is not particularly limited, but various glasses containing silica as a main component and containing oxides such as heavy metals, boron, and aluminum as required (for example, E glass, barium) Glass, lanthanum glass ceramics), various ceramics, complex oxides (for example, silica-titania complex oxide, silica-zirconia complex oxide), kaolin, clay mineral (for example, montmorillonite), mica, ytterbium fluoride, fluoride Yttrium etc. are mentioned, You may use 2 or more types together.
• Examples of commercially available inorganic particles (A) include G018-053, GM27884, 8235, GM31684 (above, manufactured by Shot Corporation), E2000, E3000 (above, manufactured by ESSTECH), and the like.
• the inorganic particles (B) may be spherical or irregular. Further, the inorganic particles (B) may be primary particles that are not aggregated or secondary particles in which primary particles are aggregated.
• the primary particle size is an average value of the major axis and the minor axis of the inorganic particles (B).
• the surface treatment method in an inorganic particle (B) spraying the solution which diluted the silane coupling agent with the solvent, stirring the inorganic particle (B) before surface treatment with a mixing tank
• examples thereof include a method of heating and drying in a tank for a certain period of time while stirring, a method of stirring and mixing inorganic particles (A) and a silane coupling agent before surface treatment in a solvent, and then drying by heating.
• the silane coupling agent is not particularly limited as long as the group represented by the chemical formula (A) and / or the group represented by the chemical formula (B) can be introduced onto the surface, but dimethyldichlorosilane, And hexamethyldisilazane.
• the material constituting the inorganic particles (B) is not particularly limited, but inorganic oxides such as silica, alumina, titania and zirconia, composite oxides, calcium phosphate, hydroxyapatite, yttrium fluoride, ytterbium fluoride, and barium titanate. And potassium titanate.
• silica, alumina, titania, silica-alumina composite oxide, and silica-zirconia composite oxide are preferable.
• Examples of commercially available inorganic particles (B) include Aerosil R812, R972, RX-50 (manufactured by Nippon Aerosil Co., Ltd.) and the like.
• the refractive index of the inorganic particles (B) is usually 1.43 to 1.50, and preferably 1.43 to 1.46.
• the difference between the refractive index after polymerization of the polymerizable monomer and the refractive index of the inorganic particles (B) is usually 0.05 or more.
• the dental curable composition may further contain a polymerization initiator.
• a redox polymerization initiator When the dental curable composition is cured at room temperature, a redox polymerization initiator can be used.
• the redox polymerization initiator is not particularly limited, and examples thereof include an organic peroxide / amine system, an organic peroxide / amine / sulfinic acid (or salt thereof) system, and the like.
• the oxidizing agent is not particularly limited, but organic peroxides such as diacyl peroxides, peroxyesters, peroxycarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, etc. Is mentioned.
• diacyl peroxides examples include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, lauroyl peroxide, and the like.
• peroxyesters examples include t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, t-butyl peroxy-2-ethylhexanoate, and the like.
• peroxycarbonates examples include t-butyl peroxyisopropyl carbonate.
• dialkyl peroxides examples include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, and the like.
• peroxyketals examples include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane.
• ketone peroxides examples include methyl ethyl ketone peroxide.
• hydroperoxides examples include t-butyl hydroperoxide.
• the reducing agent is not particularly limited, but N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N -Dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl -4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxy) Ethyl) -3,5-dimethylaniline, N, N-bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxye
• redox-based polymerization initiators include cumene hydroperoxide / thiourea-based, ascorbic acid / Cu 2+ salt-based, organic sulfinic acid (or its salt) / amine / inorganic peroxide-based oxidation-reduction, etc.
• tributylborane, organic sulfinic acid, or the like may be used.
• a photopolymerization initiator When the dental curable composition is cured by irradiation with visible light, a photopolymerization initiator can be used.
• the photopolymerization initiator is not particularly limited, and examples thereof include oxidation-reduction initiators such as ⁇ -diketone / reducing agent, ketal / reducing agent, and thioxanthone / reducing agent.
• ⁇ -diketone examples include camphorquinone, benzyl, 2,3-pentanedione and the like.
• ketals examples include benzyl dimethyl ketal and benzyl diethyl ketal.
• thioxanthone examples include 2-chlorothioxanthone and 2,4-diethylthioxanthone.
• Examples of the reducing agent include Michler's ketone, 2- (dimethylamino) ethyl methacrylate, N, N-bis [(meth) acryloyloxyethyl] -N-methylamine, ethyl N, N-dimethylaminobenzoate, 4-dimethylaminobenzoate.
• Tertiary amines such as butyl acrylate, butoxyethyl 4-dimethylaminobenzoate, N-methyldiethanolamine, 4-dimethylaminobenzophenone, N, N-bis (2-hydroxyethyl) -p-toluidine, dimethylaminophenanthol
• Aldehydes such as citronellal, lauryl aldehyde, phthaldialdehyde, dimethylaminobenzaldehyde, terephthalaldehyde; 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, 4-mercaptoacetofe Emissions, thiosalicylic acid, compounds having a thiol group such as thio benzoic acid.
• an organic peroxide may be added to the oxidation-reduction system initiator.
• a photopolymerization initiator When the dental curable composition is cured by irradiation with ultraviolet rays, a photopolymerization initiator can be used.
• the photopolymerization initiator is not particularly limited, and examples thereof include benzoin alkyl ether, benzyl dimethyl ketal, acyl phosphine oxide, and bisacyl phosphine oxide.
• Acylphosphine oxide includes 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenyl Examples include phosphine oxide, benzoylbis (2,6-dimethylphenyl) phosphonate, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, and the like.
• bisacylphosphine oxide examples include bis (2,6-dichlorobenzoyl) phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis (2,6-dichlorobenzoyl) -4.
• (bis) acylphosphine oxide may be substituted with a water-soluble substituent.
• acylphosphine oxide may be used in combination with a reducing agent such as amines, aldehydes, mercaptans, and sulfinates.
• the mass ratio of the polymerization initiator to the polymerizable monomer is usually 0.001 to 0.1, and preferably 0.002 to 0.05.
• the dental curable composition may further contain a polymerization inhibitor, an ultraviolet absorber, a fluorescent agent, a pigment and the like.
• polymerization inhibitor examples include, but are not limited to, 3,5-dibutyl-4-hydroxytoluene, hydroquinone, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, 2,6-t-butylphenol, 4-methoxyphenol, and the like. Two or more species may be used in combination.
• the dental curable composition may be a paste in which the inorganic particles (A) and the inorganic particles (B) are dispersed in the polymerizable monomer, or the polymerizable monomer that is cured. It may be a molded body in which a polymerizable monomer, inorganic particles (A) and inorganic particles (B) are dispersed in the body.
• a paste in which inorganic particles (A) and inorganic particles (B) are dispersed in a polymerizable monomer can be directly filled into the cavity of the oral cavity for treatment.
• the paste in which the inorganic particles (A) and the inorganic particles (B) are dispersed in the polymerizable monomer is cured and molded outside the oral cavity, the molded body is removed from the oral cavity using a dental adhesive. Can be installed inside.
• the composition when the dental curable composition has chemical polymerizability, or when the dental curable composition has chemical polymerizability and photopolymerizability, the composition includes an oxidizing agent and a reducing agent. It is necessary to take a packaging form in which the products are packaged separately, and to mix them immediately before using the dental curable composition.
• the dental curable composition is preferably a flowable composite resin.
• the flowable composite resin may be a single agent type or a two agent type.
• the extrusion strength of a flowable composite resin is usually 10 kgf or less. Thereby, the shapeability and operability of the flowable composite resin can be improved.
• the flowable composite resin is provided as a package having, for example, a syringe filled with the flowable composite resin, a plunger fitted into the syringe from the rear end side of the syringe, and a needle tip attached to the tip of the syringe.
• the inner diameter of the needle that the needle tip has is usually 0.3 to 0.9 mm.
• the package has, for example, two syringes connected in parallel and two plungers connected in parallel, and a static mixer is attached to the tip of both syringes. It may be provided.
• a part means a mass part.
• Amorphous barium glass particles GM27884 NanoFine180 manufactured by Schott
• A-1 Amorphous barium glass particles GM27884 NanoFine180 (manufactured by Schott) having a volume median particle size of 0.18 ⁇ m were surface-treated with 8-methacryloyloxyoctyltrimethoxysilane, and inorganic particles having a volume median particle size of 0.18 ⁇ m ( A-1) was obtained.
• inorganic particles (A-2) instead of amorphous barium glass particles GM27884 NanoFine180 (made by Schott) having a volume median particle size of 0.18 ⁇ m, barium glass particles G018-853 Ultra Fine0.4 (made by Shot) having a volume median particle size of 0.40 ⁇ m
• the inorganic particles (A-2) having a volume median particle size of 0.4 ⁇ m were obtained in the same manner as the inorganic particles (A-1), except that (2) was used.
• inorganic particles (A-3) instead of amorphous barium glass particles GM27884 NanoFine180 (manufactured by Schott) having a volume median particle size of 0.18 ⁇ m, barium glass particles G018-853 Ultra Fine 0.7 (manufactured by Schott) having a volume median particle size of 0.70 ⁇ m
• the inorganic particles (A-3) having a volume-median particle size of 0.7 ⁇ m were obtained in the same manner as the inorganic particles (A-1) except that the product (manufactured) was used.
• inorganic particles having a volume median particle size of 0.18 ⁇ m in the same manner as the inorganic particles (A-1) except that 3-methacryloyloxypropyltrimethoxysilane was used instead of 8-methacryloyloxyoctyltrimethoxysilane (A-4) was obtained.
• inorganic particles having a volume median particle size of 0.4 ⁇ m in the same manner as the inorganic particles (A-2) except that 3-methacryloyloxypropyltrimethoxysilane was used instead of 8-methacryloyloxyoctyltrimethoxysilane (A-5) was obtained.
• inorganic particles having a volume median particle size of 0.7 ⁇ m in the same manner as the inorganic particles (A-3) except that 3-methacryloyloxypropyltrimethoxysilane was used instead of 8-methacryloyloxyoctyltrimethoxysilane (A-6) was obtained.
• inorganic particles (A-7) instead of amorphous barium glass particles GM27884 NanoFine180 (manufactured by Schott) having a volume median particle size of 0.18 ⁇ m, amorphous barium glass particles 8235 Ultra Fine2.0 (manufactured by Schott) having a volume median particle size of 2.0 ⁇ m
• the inorganic particles (A-7) having a volume-median particle size of 2.0 ⁇ m were obtained in the same manner as the inorganic particles (A-1) except that the above-mentioned product was used.
• Table 1 shows the characteristics of the inorganic particles (A).
• Inorganic particles (B-1) Silica particle Aerosil R812 (manufactured by Nippon Aerosil Co., Ltd.) surface-treated with hexamethyldisilazane having an average primary particle size of 7 nm was used as inorganic particles (B-1).
• Inorganic particles (B-2) Silica particle Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) surface-treated with dimethyldichlorosilane having an average primary particle size of 16 nm was used as inorganic particles (B-2).
• inorganic particles (B-3) Silica particle Aerosil OX-50 (manufactured by Nippon Aerosil Co., Ltd.) having an average primary particle size of 40 nm was treated with 3-methacryloyloxypropyltrimethoxysilane to obtain inorganic particles (B-3) having an average primary particle size of 40 nm.
• Table 2 shows the characteristics of the inorganic particles (B).
• Example 1 2,4-bis [4- (2-methacryloyloxyethoxy) phenyl] propane (Bis-MEPP) 30.4 parts, [2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl)] dimethacrylate ( 8.7 parts of UDMA) and 4.3 parts of triethylene glycol dimethacrylate (TEGDMA) were mixed to obtain a polymerizable monomer.
• camphorquinone ethyl N, N-dimethylaminobenzoate, trimethyldiphenylphosphine oxide and dibutylhydroxytoluene (BHT) were respectively added to the polymerizable monomer to obtain a polymerizable monomer composition.
• BHT dibutylhydroxytoluene
• Example 2 A paste-like flowable composite resin was prepared in the same manner as in Example 1 except that the addition amounts of the inorganic particles (A-1) and the inorganic particles (B-1) were changed to 97.5 parts and 2.5 parts, respectively. Got.
• Example 3 The addition amounts of Bis-MEPP, UDMA, and TEGDMA were changed to 27.4 parts, 7.8 parts, and 3.9 parts, respectively, and instead of inorganic particles (A-1), inorganic particles (A-2) were changed.
• a pasty flowable composite resin was obtained in the same manner as in Example 1 except that it was used.
• Example 4 A pasty flowable composite resin was prepared in the same manner as in Example 3 except that the addition amounts of the inorganic particles (A-2) and the inorganic particles (B-1) were changed to 97.5 parts and 2.5 parts, respectively. Got.
• Example 5 A pasty flowable composite resin was obtained in the same manner as in Example 3 except that the inorganic particles (A-3) were used instead of the inorganic particles (A-2).
• Example 6 A pasty flowable composite resin was prepared in the same manner as in Example 5 except that the addition amounts of the inorganic particles (A-3) and the inorganic particles (B-1) were changed to 97.5 parts and 2.5 parts, respectively. Got.
• Example 7 A pasty flowable composite resin was prepared in the same manner as in Example 3 except that the addition amounts of the inorganic particles (A-2) and the inorganic particles (B-1) were changed to 97.0 parts and 3.0 parts, respectively. Got.
• Example 8 A pasty flowable composite resin was prepared in the same manner as in Example 3 except that the addition amounts of the inorganic particles (A-2) and the inorganic particles (B-1) were changed to 96.0 parts and 4.0 parts, respectively. Got.
• Example 9 A paste-like flowable composite resin was prepared in the same manner as in Example 3 except that the addition amounts of the inorganic particles (A-2) and the inorganic particles (B-1) were changed to 95.0 parts and 5.0 parts, respectively. Got.
• Example 10 A paste-like flowable composite resin was prepared in the same manner as in Example 1 except that the addition amounts of the inorganic particles (A-1) and the inorganic particles (B-1) were changed to 95.0 parts and 5.0 parts, respectively. Got.
• Example 11 A paste-like flowable composite resin was prepared in the same manner as in Example 5 except that the addition amounts of the inorganic particles (A-3) and the inorganic particles (B-1) were changed to 95.0 parts and 5.0 parts, respectively. Got.
• Example 12 A pasty flowable composite resin was obtained in the same manner as in Example 3 except that the inorganic particles (B-2) were used instead of the inorganic particles (B-1).
• Example 13 A pasty flowable composite resin was obtained in the same manner as in Example 9 except that the inorganic particles (B-2) were used instead of the inorganic particles (B-1).
• Example 1 A pasty flowable composite resin was obtained in the same manner as in Example 2 except that the inorganic particles (A-4) were used instead of the inorganic particles (A-1).
• Example 2 A pasty flowable composite resin was obtained in the same manner as in Example 4 except that the inorganic particles (A-5) were used instead of the inorganic particles (A-2).
• Example 3 A pasty flowable composite resin was obtained in the same manner as in Example 6 except that the inorganic particles (A-6) were used in place of the inorganic particles (A-3).
• Example 4 A pasty flowable composite resin was prepared in the same manner as in Example 3 except that the addition amounts of the inorganic particles (A-2) and the inorganic particles (B-1) were changed to 94.0 parts and 6.0 parts, respectively. Got.
• Example 5 A pasty flowable composite resin was obtained in the same manner as in Example 3 except that the inorganic particles (A-7) were used instead of the inorganic particles (A-2).
• Comparative Example 6 A pasty flowable composite resin was obtained in the same manner as in Comparative Example 2, except that the addition amounts of Bis-MEPP, UDMA, and TEGDMA were changed to 34.8 parts, 9.9 parts, and 4.9 parts, respectively. .
• Example 7 A pasty flowable composite resin was obtained in the same manner as in Example 3 except that the inorganic particles (B-3) were used instead of the inorganic particles (B-1).
• Comparative Example 8 A pasty flowable composite resin was prepared in the same manner as in Comparative Example 7, except that the addition amounts of the inorganic particles (A-2) and the inorganic particles (B-3) were changed to 96.0 parts and 4.0 parts, respectively. Got.
• Table 3 shows the characteristics of the flowable composite resins of Examples and Comparative Examples.
• Extrusion strength A cylindrical syringe made of polyolefin resin (an MI fill container having an inner diameter of 7.7 mm and a length of 78.6 mm), a cylindrical plunger and a syringe fitted into the syringe from the rear end side of the syringe Extrusion strength was evaluated using a needle tip (20G) attached to the tip.
• the needle of the needle tip has an inner diameter of 0.65 mm, a length of 13 mm, and is bent at 50 ° at a position of 7.5 mm from the tip.
• the syringe and the plunger are comprised by the member which does not transmit environmental light.
• the needle tip was attached to the tip of the syringe, and the plunger was pushed to push out the flowable composite resin from the tip of the needle tip.
• the extrusion strength was measured at 25 ° C. using a universal testing machine AG-IS (manufactured by Shimadzu Corporation). Specifically, while holding the storage container in the vertical direction, the crosshead equipped with the jig for compressive strength test is lowered at 10 mm / min and pushed out while applying a load to the flowable composite resin. The maximum load was taken as the extrusion strength. In addition, the case where extrusion strength is 10 kgf or less is set as a pass.
• a mold having a diameter of 15 mm and a thickness of 1.5 mm was filled with a flowable composite resin, and then the upper and lower sides were pressed with a slide glass.
• the floorable composite resin was cured by irradiating the upper and lower surfaces with visible light using G light prima II (manufactured by GC) for 10 seconds per point for 9 points on one side. Further, the cured product was taken out from the mold to obtain a test piece. Next, the smooth surface of the test piece was polished under dry conditions using # 600 abrasive paper.
• the ratio of the mass of the inorganic particles (B-1) to the total mass of the inorganic particles (A-2) and the inorganic particles (B-1) is 0.06. ⁇ Operability is reduced.
• the flowable composite resin of Comparative Example 5 contains inorganic particles (A-7) having a volume median particle size of 2.0 ⁇ m, the bending strength, wear resistance, abrasiveness, shapeability and operability are lowered.

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